Activating agent for improving adhesive force between yarn and rubber and application of activating agent

Abstract

The invention belongs to the field of activators, and particularly relates to an activator for improving adhesive force between yarn and rubber and application thereof. The activating agent is prepared from the following components in percentage by weight: 38 to 68 percent of a component A: alkylsilane, 24.2 to 41.2 percent of a component B: polyoxyethylene fatty acid, 5.5 to 13 percent of a component C: triethylene glycol dimethyl ether and 0.6 to 4.7 percent of a component D: alkylphenol polyoxyethylene ether. The activating agent provided by the invention can improve the adhesive force between yarns and rubber.

Description

Technical Field

[0001] The invention belongs to the field of activators, and in particular relates to an activator for improving the adhesion between yarn and rubber and a use thereof. Background Art

[0002] In the evaluation of the adhesion strength of known yarn and rubber composite materials, the yarn types are mostly conventional industrial yarns such as polyester / nylon, and the rubber types are mainly butadiene rubber, styrene-butadiene rubber, and butyl rubber. Rubber needs to be refined and reshaped before it can be used for sample production. It is commonly used in cord fabrics, canvas, and fire hoses. The bonding of yarn and rubber usually requires a traditional two-bath phenolic resin dipping system, followed by a vulcanization process. An adhesion promoter needs to be added during the one-bath dipping process. The ammonia generated by the promoter during the glue mixing process will affect the environment and human health. With the development of industrial technology, activators are widely used in the bonding process of yarn and rubber composite materials. Although the use of activators replaces the one-bath dipping process and reduces production costs, the adhesion of yarn and rubber composite materials is not ideal and cannot meet the application indicators of downstream products.

[0003] Therefore, we developed an activator formulation that can enhance the bonding performance of yarn to rubber to meet the application requirements of downstream products. Summary of the invention

[0004] The technical problem to be solved by the present invention is to develop an activator for improving the adhesion between yarn and rubber and its use, which does not require a one-bath dipping process, reduces the production process flow and reduces the production cost.

[0005] In order to achieve the above-mentioned purpose, the first aspect of the present invention adopts the following scheme: an activator for improving the adhesion between yarn and rubber, wherein the activator is composed of 38-68wt% component A: alkyl silane, 24.2-41.2wt% component B: fatty acid polyoxyethylene ester, 5.5-13wt% component C: triethylene glycol dimethyl ether and 0.6-4.7wt% component D: alkylphenol polyoxyethylene ether.

[0006] In a preferred embodiment, component A is at least one of [8-(epoxypropyloxy)-n-octyl]trimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, or 3-glycidoxypropyltriethoxysilane.

[0007] Furthermore, component A: alkyl silane is added in an amount of 56 wt %, component B: fatty acid polyoxyethylene ester is added in an amount of 30.2 wt %, component C: triethylene glycol dimethyl ether is added in an amount of 10 wt %, and component D: alkylphenol polyoxyethylene ether is added in an amount of 3.8 wt %.

[0008] The second aspect of the present invention is to provide a method for preparing the aforementioned activator, wherein component A, component B, component C and component D are fully mixed at room temperature to obtain the activator.

[0009] The third aspect of the present invention discloses a method for improving the adhesion between yarn and rubber by using the aforementioned activator, comprising the processes of oil activation on the yarn, yarn aging, dipping and vulcanization; wherein the yarn is a high modulus low shrinkage polyester industrial yarn with a fineness of 800D-1500D.

[0010] In a preferred embodiment, the spinning oiling rate is 0.25-0.35%, and oiling refers to adding an activator.

[0011] Furthermore, heat treatment is used during aging, the aging temperature is 60-80° C., and the aging time is 24-72 hours. The dipping is a one-time dipping.

[0012] The fourth aspect of the present invention is to provide the use of the aforementioned activator in improving the adhesion between yarn and rubber, and the use of the aforementioned preparation method in improving the adhesion between yarn and rubber.

[0013] Compared with the prior art, the present invention has the following beneficial effects: the hydroxyl groups on the alkyl silane increase the bonding force with the active components on the rubber, and the hydroxyl groups and the active components of the dipped rubber undergo an aldol condensation reaction, thereby promoting the bonding between the rubber and the yarn.

[0014] Among them, alkyl silane is used as an activator to completely replace epoxy resin for the first time. Together with fatty acid polyoxyethylene ester, triethylene glycol dimethyl ether and alkylphenol polyoxyethylene ether, the four together improve the adhesion between yarn and rubber. DETAILED DESCRIPTION

[0015] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0016] The invention discloses an activator for enhancing the bonding performance between yarn and rubber, comprising component A (alkyl silane) + component B (fatty acid polyoxyethylene ester) + component C (triethylene glycol dimethyl ether) + component D (alkylphenol polyoxyethylene ether). Components A, B, C and D are all commercially available.

[0017] The present invention also discloses a method for improving the adhesion between yarn and rubber by using an activator, comprising the following steps:

[0018] (1) Yarn oiling and activation: After spinning is completed on the TMT machine, oil is applied before winding. During the oiling process, the injection pump oil nozzle is oiled and the oiling rate is set to 0.25-0.35% (activator formula); (2) After winding, the yarn is aged: After spinning on the TMT machine, it needs to be aged in a constant temperature box, and the aging temperature and time are 60-80°C and 24-72h; (3) Dipping: After twisting, the yarn is dipped in glue (RFL glue), and the dipping time is 195s; because the modulus and polarity between the fiber (yarn) and rubber are very different, the bonding force between untreated fiber and rubber is generally low. Chemical bonding is the result of the formation and action of chemical bonds, which plays a key role in the bonding between the skeleton material and the T rubber. This bonding is mainly caused by the formation of a macromolecular network between the RFL glue (resorcinol + formaldehyde (catalyst: ammonia water) → meta-formaldehyde resin liquid + latex → dipping liquid RFL, which is commercially available) and the rubber. Under certain temperature conditions, the rubber begins to soften, and the various chemical components in the rubber begin to become active, partially diffusing and penetrating to the fiber surface. These chemical substances react chemically with RFL to form a macromolecular network structure, and the fiber and rubber are bonded through chemical bonding. After surface activation treatment, the polyester fiber reacts chemically with the RFL adhesive, and then cross-links with the styrene-butadiene rubber during the vulcanization stage; (4) Vulcanization process: Set the parameters of the flat vulcanizer to 150-165°C, 3.2-3.7MPa, 16-24min or 150-165°C, 115-145KN, 16-24min. After the temperature stabilizes, place the mold on the vulcanizer for vulcanization molding. After vulcanization molding, it can be used as tire cord; (5) Peel force value and extraction force value test, Peeling force value: Cut the formed samples, if the original yarn is ≤1670dtex, cut one on each side and keep 5 in the middle for testing; if the original yarn is ≥1670dtex, cut two on each side and keep three in the middle for testing; Extraction force value test: Cut off the edge of the cooled sample, and finally trim it into an "H" shape with a yarn shear. Each cord can be cut into 5 parallel specimens. Put the sample on the fixture, zero the gauge length before starting the first sample test, and the load needs to be zeroed before each sample test, and then start the test.

[0019] The present invention is further illustrated by specific examples. In the following examples and comparative examples, the vulcanization process parameters are: 160°C, 135KN, 20min. Unless otherwise specified, the yarn physical properties are: linear density / (dtex): 1120, linear density CV / (%): 1.40, breaking strength / (N): 76.0, breaking strength / (cN / dtex): 7.00, breaking strength CV / (%): 3.00, breaking elongation / (%): 13.0, breaking elongation CV / (%): 8.0, medium elongation 4.0 (cN / dtex / %): 5.8, dry heat (177°C*10min*0.05) (cN / dtex / %): 2.60, DSI: 8.4, network degree (crochet method) / (nodes / m): 6.

[0020] Example 1

[0021] The activator preparation comprises the following steps:

[0022] 1. Mix component A (alkyl silane, 38-68wt%) + component B (fatty acid polyoxyethylene ester, 24.2-41.2wt%) + component C (triethylene glycol dimethyl ether, 5.5-13wt%) + component D (alkylphenol polyoxyethylene ether, 0.6-4.7wt%) of the activator formula evenly at room temperature.

[0023] 2. Change the type of component A in step 1 to [8-(epoxypropyloxy)-octyl]trimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane and 3-glycidyloxypropyltriethoxysilane, and the contents of components A, B, C and D are 56%, 30.2%, 10% and 3.8%, respectively, to obtain new formulas, which are recorded as formulas E, F and G, respectively.

[0024] The component contents involved in this article are all mass fractions.

[0025] Example 2

[0026] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0027] (1) Activator formulations E, F and G were used in the spinning process, and the oil loading rate was set to 0.31%;

[0028] (2) The aging temperature and time of the yarn were 75 °C and 48 h, respectively;

[0029] (3) Formed through the process of dipping and vulcanization;

[0030] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0031] Table 1 Effect of activator formulations E, F and G on the adhesion between yarn and rubber

[0032] Activator formula E F G Extraction force(N) 166.01 182.68 162.84 Peel force value (N) 96.93 115.82 89.17

[0033] As can be seen from Table 1, activator formula F has better extraction force and peeling force values.

[0034] Example 3

[0035] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0036] (1) The activator formula F was used in the spinning process, the content of component A was 38%, 44%, 50%, 56%, 62% and 68% respectively, the content of components C and D remained unchanged, the content of component A+B was maintained at 86.2%, and the oiling rate was set to 0.31%;

[0037] (2) The aging temperature and time of the yarn were 75 °C and 48 h, respectively;

[0038] (3) Formed through the process of dipping and vulcanization;

[0039] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0040] Table 2 Effect of the content of component A in the activator F formula on the adhesion between yarn and rubber

[0041]

[0042] From Table 2, it can be seen that when the content of component A in the activator F formula is 56%, it has better extraction force and peeling force values. And the content of component A in the activator F formula has a greater impact on the extraction force and peeling force values.

[0043] Example 4

[0044] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0045] (1) The activator formula F was used in the spinning process, the contents of component B were 24.2%, 27.2%, 30.2%, 33.2%, 36.2% and 41.2%, respectively, the contents of components C and D remained unchanged, the content of component A+B was maintained at 86.2%, and the oiling rate was set to 0.31%;

[0046] (2) The aging temperature and time of the yarn were 75 °C and 48 h, respectively;

[0047] (3) Formed through the process of dipping and vulcanization;

[0048] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0049] Table 3 Effect of the content of component B in the activator F formula on the adhesion between yarn and rubber

[0050]

[0051] From Table 3, it can be seen that when the content of component B in the activator F formula is 30.2%, it has better extraction force and peeling force values. And the content of component B in the activator F formula has a greater impact on the extraction force and peeling force values.

[0052] Example 5

[0053] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0054] (1) The activator formula F was used in the spinning process, the content of component C was 5.5%, 7.0%, 8.5%, 10%, 11.5% and 13%, the content of components A and B remained unchanged, the content of component C+D was maintained at 13.8%, and the oiling rate was set to 0.31%;

[0055] (2) The aging temperature and time of the yarn were 75 °C and 48 h, respectively;

[0056] (3) Formed through the process of dipping and vulcanization;

[0057] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0058] Table 4 Effect of the content of component C in the activator F formula on the adhesion between yarn and rubber

[0059]

[0060] It can be seen from Table 4 that when the content of component C in the activator F formula is 10%, it has better extraction force and peeling force values.

[0061] Example 6

[0062] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0063] (1) Activator formulation F was used in the spinning process, with the contents of components A, B, C and D being 56%, 30.2%, 10% and 3.8%, respectively, and the oil loading rates being set to be 0.25%, 0.27%, 0.29%, 0.31%, 0.33% and 0.35%, respectively;

[0064] (2) The aging temperature and time of the yarn were 75 °C and 48 h, respectively;

[0065] (3) Formed through the process of dipping and vulcanization;

[0066] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0067] Table 5 Effect of oiling rate on the adhesion between yarn and rubber

[0068]

[0069] From Table 5, it can be seen that when the oil uptake rate of the yarn is 0.31%, the activator formula F has better extraction force and peeling force values.

[0070] Example 7

[0071] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0072] (1) Activator formulation F was used in the spinning process. The contents of components A, B, C and D were 56%, 30.2%, 10% and 3.8%, respectively, and the oil loading rate was set to 0.31%.

[0073] (2) The aging temperatures of the yarn were 60°C, 65°C, 70°C, 75°C and 80°C for 48 h;

[0074] (3) Formed through the process of dipping and vulcanization;

[0075] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0076] Table 6 Effect of aging temperature on the adhesion between yarn and rubber

[0077] Yarn aging temperature 60℃ 65℃ 70℃ 75℃ 80℃ Extraction force(N) 155.53 167.81 171.89 182.68 171.11 Peel force value (N) 79.30 85.01 93.55 115.82 105.51

[0078] It can be seen from Table 6 that when the aging temperature of the yarn is 75°C, the activator formula F has better extraction force and peeling force values.

[0079] Example 8

[0080] The present invention discloses a method for improving the adhesion performance between yarn and rubber by using an activator formula, comprising the following steps:

[0081] (1) Activator formulation F was used in the spinning process. The contents of components A, B, C and D were 56%, 30.2%, 10% and 3.8%, respectively, and the oil loading rate was set to 0.31%.

[0082] (2) The yarn aging temperature was 75 °C and the aging time was 24 h, 36 h, 48 h, 60 h and 72 h respectively;

[0083] (3) Formed through the process of dipping and vulcanization;

[0084] (4) The extraction force and peeling force values ​​were tested respectively. The specific test results are shown in the following table:

[0085] Table 7 Effect of aging time on the adhesion between yarn and rubber

[0086] Yarn aging time 24h 36h 48h 60h 72h Extraction force(N) 160.32 173.74 182.68 181.52 180.10 Peel force value (N) 99.59 106.55 115.82 115.30 114.51

[0087] It can be seen from Table 7 that when the aging time of the yarn is 48h, the activator formula F has better extraction force and peeling force values.

[0088] Example 9

[0089] (1) Activator formula F was used in the spinning process, the contents of components A, B, C and D were 56%, 30.2%, 10% and 3.8% respectively, and the oiling rate was set to 0.31%. The yarn linear density was 2240 dtex.

[0090] (2) The yarn aging temperature is 75°C and the time is 48 h;

[0091] (3) Formed through the process of dipping and vulcanization;

[0092] (4) Test the extraction force and peeling force respectively.

[0093] Table 8 Effect of yarn linear density on rubber adhesion

[0094] Yarn linear density (dtex) 1120 2240 Extraction force(N) 182.68 191.87 Peel force value (N) 115.82 157.16

[0095] When the yarn fineness is higher, the pull-out force and peeling force values ​​are also higher.

[0096] Comparative Example 1

[0097] Compared with the activator formula of Example 2, component A was replaced with epoxy resin (glycerol glycidyl ether). The rest of the process was the same as Example 2. The extraction force and peeling force were tested, and the results were 172.24N and 107.2N respectively.

[0098] From Comparative Example 1, it can be seen that the use of epoxy resin as an activator has a lower bonding strength between the yarn and the rubber than the use of alkyl silane as an activator. In the prior art, epoxy resin is used as an activator. The epoxy resin needs to undergo a ring-opening reaction to expose the active sites before it can undergo a polymerization reaction with the dipping solution and then vulcanize with the rubber. Alkyl silane does not need to open the ring, and can polymerize more fully with the dipping solution under the same conditions, thereby increasing the bonding strength between the yarn and the rubber.

[0099] Comparative Example 2

[0100] Compared with the activator formula F of Example 2, component B is omitted, and the mass ratio of components A, C, and D is 56:10:3.8, and the three are mixed at room temperature to form an activator. The rest of the process is the same as Example 2. The extraction force value and the peeling force value are tested, and the test results are 134.16N and 79.23N respectively.

[0101] Comparative Example 3

[0102] Compared with the activator formula F of Example 2, component C and component D are omitted, and the mass ratio of component A to component B is 56:30.2, and the two are mixed at room temperature to form the activator. The extraction force and peeling force values ​​are tested, and the test results are 72.39N and 56.18N respectively.

[0103] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which are all covered by the protection scope of the present invention.

Claims

1. An activator for improving the adhesion between yarn and rubber, characterized in that: The activator is composed of 38-68wt% of component A: alkyl silane, 24.2-41.2wt% of component B: fatty acid polyoxyethylene ester, 5.5-13wt% of component C: triethylene glycol dimethyl ether and 0.6-4.7wt% of component D: alkylphenol polyoxyethylene ether.

2. An activator for improving the adhesion between yarn and rubber as claimed in claim 1, characterized in that: Component A is at least one of [8-(epoxypropyloxy)-n-octyl]trimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane.

3. An activator for improving the adhesion between yarn and rubber as claimed in claim 1, characterized in that: Component A: the addition amount of alkyl silane is 56wt%, component B: the addition amount of fatty acid polyoxyethylene ester is 30.2wt%, component C: the addition amount of triethylene glycol dimethyl ether is 10wt%, and component D: the addition amount of alkylphenol polyoxyethylene ether is 3.8wt%.

4. A method for preparing the activator according to any one of claims 1 to 3, characterized in that: The components A, B, C and D are fully mixed at room temperature to obtain an activator.

5. A method for improving the adhesion between yarn and rubber using the activator according to any one of claims 1 to 3, characterized in that: The process includes yarn oil activation, yarn aging, dipping and vulcanization; the yarn is high modulus low shrinkage polyester industrial yarn with a fineness of 800D-1500D.

6. A method for improving the adhesion between yarn and rubber according to claim 5, characterized in that: The spinning oiling rate is 0.25~0.35%, and oiling refers to the addition of activator.

7. A method for improving the adhesion between yarn and rubber according to claim 5, characterized in that: Heat treatment is used during aging, the aging temperature is 60~80℃, and the aging time is 24~72 hours.

8. A method for improving the adhesion between yarn and rubber according to claim 5, characterized in that: The dipping is a one-time dipping.

9. Use of the activator according to any one of claims 1 to 3 in improving the adhesion between yarn and rubber.

10. Use of the preparation method according to claim 4 in improving the adhesion between yarn and rubber.

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